Process for dyeing thermoplastics in the melt

ABSTRACT

Process for dyeing thermoplastics in the melt, characterised by the use of a dyestuff of the formula   wherein A1 and A2 denote anthraquinonoid radicals and B denotes a carbocyclic or heterocyclic aromatic radical in which the imino groups are directly bonded to a benzene ring. Fast red to blue colorations are obtained.

United States Patent [191 Jost et al. Dec. 2, 1975 [54] PROCESS FOR DYEING THERMOPLASTICS 2,571,319 10/1951 Waters et al. 260/40 P IN THE MELT 2,585,682 2/1952 Randall et al.... 260/367 2,908,684 10/1959 Martin et a1. 260/368 X [75] Inv nt rs: M J st, Oberwil; Arnold Wick, 3,671,176 6/1972 Kaufmann et a1. 260/367 x Therwil, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley, Primary Examiner M' welsh Assistant Examiner-S. M. Person Attorney, Agent, or FirmVincent J. Cavalieri [22] Filed: Aug. 20, 1973 [21] Applt No.: 389,909 [57] ABSTRACT Process for dyeing thermoplastics in the melt, charac- [301 Foreign Application Priority Data terised by the use of a dyestuff of the formula Aug. 29, 1972 Switzerland 12753/72 H H [52] US. Cl. 260/40 P; 260/37 P; 260/37 NP I 51 Int. cl. C08K 5/08 [58] Field of Search 260/367, 368, 40 P, 37 P,

, 2 0/37 p wherein A and A denote anthraquinonoid radicals and B denotes a carbocyclic or heterocyclic aromatic 5 References Cited radical in which the imino groups are directly bonded UNITED STATES PATENTS to a benzene ring. Fast red to blue colorations are 0b 12 1,684,327 9/1928 Mieg et a1 t 260/367 amed 2,076,197 4/1937 Gutzwiller 260/367 X 10 Claims, No Drawings PROCESS FOR DYEING THERMOPLASTICS IN THE MELT is heated to a temperature above the melting point of the polyester, that is to say converted into a melt, and this molten state is maintained for at least minutes and in many cases substantially longer; i

In addition to possessing heat resistance, the dyestuffs usable for the bulk dyeing of polyesters must also have the necessary compatibility towards the polyester melt, which is heated to at least 275C.

A further requirement of the dyestuffs is fastness to sublimation, that is to say the dyestuffs must neither sublime out of the molten polyester moulding composition nor out of the moulded end product.

Hitherto, only few dyestuff categories have been disclosed which are equal to these extreme requirements.

It has now been found that anthraquinone dyestuffs of the formula wherein A and A denote anthraquinonoid radicals and B denotes a carbocyclic or heterocyclic aromatic radical in which the imino groups are directly bonded to a benzene ring, are outstandingly suitable for dyeing thermoplastics in the melt.

Dyestuffs of particular interest are those of the formula wherein B has the indicated meaning, one X, denotes an H atom or a hydroxyl, alkoxy, arylmercapto, arylamino, benzthiazolylmercapto or acylamino, especially benzoylamino, group and the remaining X denote H atoms, one Z denotes an H atom or Cl atom and the other denote H atoms. The radicals A and A denote, for example, the radicals of l-aminoanthraquinone, lamino-3-chloroanthraquinone, l-amino-6- or 7-chloroanthraquinone, 1amino-4-hydroxyanthraquinone, lamino-4-methoxyanthraquinone, l-amino5- methoxyanthraquinone, 1amino-4-phenoxyanthraqui- 2 none, lamino-4-phenylmercaptoanthraquinone, 1- amino-S-phenylmercaptoanthraquinone, 1 l-amino-8- phenylmercaptoanthraquinone, l-amino-4- phenylaminoanthl a-quinone, l-amino-4-benzoylaminoanthraquinone, l-am-ino-4-(2,3'- or 4- chlorobenzoylamino )-anthraquinone, l-amino-S-benzoylaminoanthraquinone, l-amino-5-(2,3- or 4- chlorobenzoylamino)-anthraquinone, l-amino-8-benzoylaminoanthraquinone l-amino -4-benzthiazolylmercaptoanthraquinone and l-amino-S-benzthiazolylmercaptoanthraquinone.

As further anthraquinonoid radicals there may be mentioned anthraquinone or anthrone radicals which contain a fused benzene ring or hetero-ring, such as, for example, the benzanthrone, .pyrazolanthrone, isotliiazolanthrone or-anthrapyridone radicals. As examples, there may be mentioned the radicals of pyrazolanthrone; 5aminoisothiazolanthrone, '6-amino-3- methylanthrapyridone, 3-aminobenzanthrone or 4- aminoanthraquinone-Z, l (N), 1 ',2 '-(N )-benzacridone.

Possible aromatic radicals B are:

a. mononuclear or polynuclear aryl radicals, such as phenylene, naphthylene, anthracene or chrysene radicals.

b. Polyaryl radicals of the formula wherein B, and B denote aryl radicals, for example naphthylene or especially phenylene radicals, n denotes the number 13 and X denotes a direct bond or a bridge, for example an O atom or S atom or an imino, CO-, COCO, SO alkylene-, N= NHCO- or ORO group, wherein R represents an alkylene or arylene group. X can also denote a heterocyclic radical, for example an oxdiaz ole or triazole radical.

c. Arylene radicals which contain a fused hetero-ring, for example a furane, thiophene, pyrrole, oxazole, thiazole, pyridine or pyrimidine ring or a cycloaliphatic S-membered or 6-membered ring such as, for example, a fluorene or fluoroanthene radical.

As bridge members of the groups (a) there may preferably be mentioned those of the formula wherein Y denotes an H atom or a nitro group, an alkyl or alkoxy group containing 1-6 carbon atoms, an aralkoxy group, an arylsulphonyl or alkylsulphonyl group or a phthalimino group and Z denotes an H atom or an alkyl or alkoxy group, and especially those of the formula wherein Q denotes a SO or especially CO-- group and R denotes an alkyl radical containing 1-6 carbon atoms, or a phenyl, naphthyl or diphenyl radi- 3 4 7 Cal. 1 As bridge members of group (0) there may preferably As bridge members of the groups b) there may prefbe mentioned those of the formula erably be mentioned those of the formula r s :5 3 s wherein X has the indicated meaning, U denotes a diwherein X X Y and Y denote H or nitro groups, rect bond or an O or S atom and V denotes an O or S alkyl or alkoxy groups containing l-6 carbon atoms or 15 atom or animino, CO, CH or SO group, a phthalimino group and X denotes a direct bond or a that is to say, for example, the radicals of fluorene, flubridge, for example an O or S atom, an imino, keto, sulorenone, diphenyl oxide, diphenylsulphone, carbazole,

phone or alkylene group, preferably a methylene or thianthrene or xanthone.

ethylene group, or a group of the formula COalk- The radicals B in the formula (ll) preferably denote yleneCO, 20 naphtylene,' fluorene, l ,9-anthracene, perinaphthene,

(wherein X denotes -NH-phenyl or phenyl) -NHCOCONH, mucmU-couw,

3 l -CONH NHCO- N HNCO CONH (X and Z H halogen alkyl or alkoxy) 5 6 carbazole, N-alkylcarbazole, xanthene, thianthrene, 1 X 0 NH diphenylene oxide, diphenylene sulphide or the radical of the formula Z Z 00/ x i) x Dyestuffs of particular interest are those of the for- 10 mula I (VI) X 0 NH 1 l lN B g X 8 l (3 X Z wherein B B X, X and Z have the indicated mean- 25 wherein X, and Z have the indicated meaning, in the ings, as well as dyestuffs of the formula molar ratio of 2: l with a corresponding dihalogenoaryl x o HN- Q I n i II I m I I Z I II I 1 0 i n l wherein Q and X and Z have the indicated meaning, compound, especially a dihalogenoaryl compound of and also those of the formula the formula z Z Z ll X 0 X Z ,I II I Z wherein Q, X, and Z have the indicated meaning. Y The dyestuffs to be used according to the invention Hal are in part known compounds and can be obtained ac- Hal cording to known processes. 60

The dyestuffs containing a bridge member of group Z (a), that is to say a mononuclear or polynuclear aryl wherein Y and Z have the indicated meaning. radical, are obtained, for example, by condensation of The following dihalogen compounds may be menan aminoanthraquinone, especially an aminoanthraquitioned as examples: 1,4-dichlor0benzene, 2,4- none of the formula dichloronitrobenzene, 1,4-dibromobenzene, 1,3-

dibromobenzene, 2,4-dichlorotoluene, 2,6- dichloroanisole, 2,4-dichloroanisole, 2,4-dichloro-4- nitrodiphenyl ether, 2,4-dichloroacetophenone, 2,5- dichloroacetophenone, 2,4-dichloro-wphenylacetophenone, 2,5-dichloro-w-phenylacetophenone, 1,4-dichloronaphthalene, 1,5-dichloronaphthalene, 1,5-dibromonaphthalene, 2,6-dibromonaphthalene, 9,10-dibromoanthracene, 2,8-dichlorochrysene, 2,8-dibromochrysene and 4,1 l-dibromofluoroanthene.

Dihalogen compounds of particular interest are those of the formula Hal Hal

Hal

wherein X, Hal and n have the indicated meaning.

The following dihalogenodiaryl compounds may be mentioned as examples: 4,4-dichlorodiphenyl, 4,4'- dibromodiphenyl, 3,3-dichlorodiphenyl, 4,4'- dichloro-3 ,3 -dimethyldiphenyl, 4,4'-dichlorodiphenylmethane, 4,4-dibromodiphenylmethane, 4,4'- dichloro-l ,Z-diphenylethane, 4,4-dichlorol,ldiphenylethane, 4,4-dichlorobenzil, 4,4'-dibromobenzil, 2,2-dichlorobenzil, 3,3- or 4,4'-dichloroazobenzene, 4,4-dibromodiphenyl ether, l,4-bis[4-bromophenoxy]-benzene, 4,4'-dibromodiphenylamine, 4,4- dichlorodiphenylsulphide, 3,3-dichlorodiphenylsulphone, bis-(4-chlorophenyl)-sulphoxide, bis-(4-chloro- 2-nitrophenyl)-sulphide, bis-(4-chlorophenyl)-terephthalic acid diamide, 2,4'-dichlorobenzophenone, 3,4- dichlorobenzophenone, 3,3f-dibromobenzophenone, 4,4'dichlorobenzophenone, 4,4-dichloro-3-nitro-benzophenone, 1,4-bis[4-bromobenzoyl]-benzene, 4,4'- bis[4"-chlorobenzoyl]-diphenyl, l,5-bis[4'-chlorobenzoyl]-naphthalene, 2,5-bis[4-chlorobenzoyl]-thiophene, 2,3-dichlorodiphenylsulphone, 2,4- dichlorodiphenylsulphone, 4,4dichlorodiphenylsulphone, 4,4'-dibromodiphenylsulphone, 1,2-bis-(4'- chlorobenzoyl)benzene, l,3-bis-(4-chlorobenzoyl)- benzene, 2,4-dichlorophenyl-a-naphthyl-sulphone, 2,S-dichlorophenyl-oz-naphthyl-sulphone, l,3-bis-(4- chlorophenylsulphonyl)-benzene, l,4-bis-(4'-chlorophenylsulphonyl)-benzene, 4,4'-bis-(4"-chlorophenylsulphonyl)-diphenyl as well as the compounds of the formulae (31- -so -co- The dyestuffs containing a bridge member of the group (c) are obtained advantageously by condensation of an aminoanthraquinone, especially of an aminoanthraquinone of the formula (VI), in the molar ratio of 2:1 with a dihalogen compound of the formula Hal Hal wherein Hal, U, V and X have the indicated meanings.

The following dihalogen compounds may be mentioned as examples: 2,7-dibromofluorene, 2,7-dichloro-' compounds.

Thermoplastics which can be dyed with the dyestuffs mentioned are polystyrene and its copolymers, polycarbonates and polyamides, but especially linear polyesters.

As linear polyesters there may especially be mentioned those which are obtained by polycondensation of terephthalic acid or its esters with glycols of the formula HO(CH ),,Ol-l, wherein n denotes the number 2-10, or with l,4-di(hydroxymethyl)-cyclohexane, or by polycondensation of glycol ethers of hydroxybenzoic acids, for example p-(B-hydroxyethoxy)benzoic acid. The term linear polyesters also includes copolyesters which are obtained by partial replacement of the terephthalic acid by another dicarboxylic acid or a hy- EXAMPLE 1 Non-delustered polyethylene terephthalate granules suitable for the manufacture of fibres are shaken with 1% of the dyestuff of the formula 0 I l I II II ll 0 0 droxycarboxylic acid and/or by partial replacement of in a vessel which can be closed, on a shaking machine,

the glycol by another diol.

However, polyethylene terephthalates are of particular interest.

The linear polyesters to be dyed are appropriately intimately mixed, in the form of powders, chips or granules, with the dyestuff. This can be done, for example, by sprinkling the polyester particles with the finely divided dry dyestuff powder or by treating the polyester particles with a solution or suspension of the dyestuff in an organic solvent and subsequently removing the solvent.

Finally, the dyeing substance can also be added directly to the molten polyester or be added before or during the polycondensation of the polyethylene terephthalate.

The ratio of dyestufi to polyester can vary within wide limits depending on the desired colour strength. in general, it is advisable to use from 0.01 to 2 parts of dyestuff per 100 parts of polyester.

The polyester particles treated in this way are melted in an extruder according to-known processes and extruded to give articles, especially films or fibres, or cast to give sheets.

Uniformly and intensely dyed articles of high fastness to light or to migration are obtained. The dyed fibres obtainable according to the process are furthermore distinguished by excellent fastness to wet processing and to dry cleaning.

A particular advantage of the dyestuffs to be used according to the invention is that they dissolve in the for 15 minutes. The uniformly dyed granule particles are spun on a melt spinning installation (285C 1 3C, dwell time in the spinning machine approx. 5 minutes) to give filaments which are stretched, and wound up, on a stretch-and-twist installation. Because of the solubility of the dyestuff in polyethylene terephthalate, a vivid red dyeing is obtained, which is distinguished by outstanding fastness to light, excellent fastness to washing, dry cleaning, overdyeing and sublimation and high stabilityto chlorite bleach.

The dyestuff used in this example can be obtained as follows:

44.4 parts of l,4-bis[4'-bromobenzoyl]-benzene, 47 parts of l-aminoanthraquinone, 2 parts of copper-(l) chloride, 40 parts of sodium carbonate and 1,800 parts of nitrobenzene are stirred for 15 hours at the boil. The

resulting precipitate is filtered off after cooling the mixway, 67 parts of red-brown powder are obtained, which dissolves in concentrated sulphuric acid to give a brown colour and on dilution with water separates out again in red flocks.

EXAMPLES 2 ll The table which follows lists, in Column I, further dyestuffs which are used according to the process indicated in Example 1 for dyeing polyethylene terephthal- Sh ade of the PBS d eing Example Dvestigfs scarlet-red Continued Shade of the PES dveing Dyestuffs Example red violet dark red I -m w v red 15 16 C0ntinued Examnle Dyestuffs Shade of the PBS dveinz II I 1 I! II J U 0 NH O i P 8 .x r 2 ll dark red I H H I I 1311 o 0 NH n 1 O NH 0 NH- -co- -co- 4m 0 I! dark red I H l v f 0 0 NH Continued Example Dyestuffs v Shade of the PES dyeing 11 ff -coblue -CO--NH o i ll 1' i 0 NH I CO 1 u I NH ate. Column II indicates the shade of the dyed fibre. 20 condensation of 1 mol of the corresponding The dyestuffs used in these examples can be obtained dihalogenoarylketone with 2 mols of the corresponding according to the process indicated in Example 1 by aminoanthraquinone.

Example 7' Dyestuffs Shade of the Manufactured I PES dyeing accordim to bltii sh-t-inged DRP. 215 294 o NH-@-NH 0 red 1 XI ll 0 O @""Q l3 8 13H JH 0 red DRP 220,579

I ll 0 O O NH- -C -N O 7 1Q, it i Co 1 n I red DRP 222,205

" (In 0 O CO CO ,2 I 15 O N NH o claret DRP 230,400 i II 1'9 20 I Comi nu ed 2 Example Dyestuffs v Shade of the Manufactured PBS dv'eing 1 "according; to

16 1 2 9' red v DRP 230, +11

7 f? 9 violet-fed DRP 23o,ao9

--NH 0 $2 Q 18 blue-green DRP 25O, +O9.

n v 1 0 NH NH 0 NH O X! v l9 violet DRP 250,409

Continued Dyestuffs 28 H I m n Example Shade of the PBS dy i Manufactured accordi g to DRP 2 +1, 5

29 0 NH 0 3 8 blue u k i H o NH NH 0 v H 30 0 I brow-red H *1 0 I? co-{i} .00

E'a S 31 0 NH O grey O NH NF 0 Co 32 brown Continued Example Dyestuffs Shade of the PES dv dark red 34 v I gfey-blue -NH 0 I y A w @O@ 3 in o I o 55 o NH-@-(1--NH o 7 claret n I I I n N w I X 13 3 3 :53

1 Ex- Shade 01 amp]. Dyestuffs the PES dyeing 5 red 37 wings -C0ntinued Ex- Shade of ample Dyestuffs the PES dyeing 3s 0 NH-@-so -@so -@NH Orange II 0. o

39 0 NH- ?-SO -@GH orange ll ll 0 40 if NH E orange II 0 ll 41 red 42 red 43 blue C0ntinued EX- shade 0f ample Dyestuffs the PES dyeing 44 o NH@CO-@@CO-NHO red u n T O NH Q @im 45 0 NH-@ct)@-c0-@-NH red u o z;

c1 46 o NH@co co-@-NH red reaction at 190C) 47 0 ZF red' C CH 48 i 3 rt d Continued Shade of ample Dyestuffs the PES dyeing 49 O NH OCH dark ll olive o ll II 0 NH ll O N0 50 0 NH -@CO@NH brown II II 0 N0 NH CO yellow- 51 O brown NH ll 0 52 0 NH TQF00 N0 brown 0 o ll 0 CO CO N 53 0 NH@CO2Q brownll NH red 0 II II 0 C0ntinued Ex- I Shade of] ample Dyestuffs the PES 1 dyeing T0 0 NH O N H w \Z I red,

0 II II 6O 0 NH@o-@no n I 2 red NH I! II 0 61 0 NH blue I! g I 62 O g' o orange ll ll ll C1 C1 II 0 v 0 (reaction at 170C) 63 0 NH o brown Ii ll II II 0 O NH t 64 0 8 claxe n e E e n 2 It 0 I ll C0ntinued Ex- Shade of ample Dyestuffs the PES dyeing NH 65 O 8 brown Cl 0 Cl ll 66 O NHCH -@NH blue II II ll ll 0 T 0 v 6'7 0 NH red 0 NH ll n 0 ll 0 68 0 @f O red ll ll 0 O 69 0 NH NHO velar-e15 N co co O 2 g 0 NH 70 0 2 orangell brown 

1. A PROCESS FOR DYEING A THERMOPLASTIC IN THE MELT CHARACTERISED BY THE USE OF A DYESTUFF OF THE FORMULA
 2. Process according to claim 1, characterised in that a dyestuff of the formula
 3. Process according to claim 1, characterised in that a dyestuff of the formula
 4. Process according to claim 1, characterised in that a dyestuff of the formula
 5. Process according to claim 1, characterised in that the dyestuff of the formula
 6. Process according to claim 1, characterised in that the dyestuff of the formula
 7. Process according to claim 1, characterised in that the dyestuff of the formula
 8. Process according to claim 1, characterised in that a linear polyester is used as the thermoplastic.
 9. The dyed polyester consisting essentially of the product obtained according to the process of claim
 8. 10. The dyed thermoplastic consisting essentially of the product obtained according to the process of claim
 1. 